Modified pressure sensitive adhesive

ABSTRACT

A modified pressure sensitive adhesive (PSA) is produced by polymerizing at least one ethylenically unsaturated monomer to form a base polymer and reacting the base polymer with a modifying polymer comprising units derived from a n-vinyl lactam to thereby produce a modified polymer. The modified polymer can be used to form modified PSAs having improved adhesion properties over PSAs formed from the unmodified base polymer.

FIELD OF THE INVENTION

The invention relates to modified pressure sensitive adhesives (PSAs)having improved adhesion properties. In another aspect, the inventionconcerns a novel process for producing such modified PSAs. The inventivemodified PSAs are useful as, for example, tapes, labels, stickers,decals, decorative vinyls, laminates, and wall coverings.

BACKGROUND OF THE INVENTION

Pressure sensitive adhesives (PSAs) are useful in many applications forbonding a flexible material to another surface. PSAs may be classifiedaccording to the chemical composition (i.e., the main elastomer) used inthe adhesive formulation. The largest class of PSAs in use today arepolyacrylates. A distinct and advantageous feature of polyacrylates isthat they are tacky without compounding with tackifying resins. Afurther advantage is that polymerization of acrylic monomers does notrequire expensive equipment.

Acrylic PSAs are typically produced either by emulsion or solutionpolymerization. Emulsion polymerization is by far the most importantprocess for producing acrylic PSAs because acrylic dispersions areenvironmentally safe, easy to handle, and economical. Further, acrylicdispersions from emulsion polymerization exhibit good adhesiveproperties, coatability at very high speeds, and favorable die-cuttingproperties.

The adhesion properties of the acrylic PSA dispersions resulting fromemulsion polymerization are greatly influenced by the type and relativequantities of monomers employed in the polymerization process. Mostpressure sensitive acrylic adhesives are formed from acrylic esters thatyield soft tacky polymers of low glass transition temperature (T_(g)).The primary monomers used to form acrylic PSAs are alkyl acrylates andmethacrylates of 4 to 17 carbon atoms. In particular, butyl acrylate,2-ethylhexyl acrylate, and iso-octyl acrylate are known monomers whichcan be polymerized to yield soft and tacky homopolymers. However,homopolymers are not generally used for pressure sensitive adhesives.Rather, homopolymers are typically modified by copolymerization with-atleast a small portion of other comonomers. Copolymerization with othermonomers is a universally used technique to vary adhesive properties.Typically, the main monomer (i.e., alkyl acrylates and methacrylates of4 to 17 carbon atoms) are copolymerized with a modifying monomer(typically a second acrylic ester) and/or monomers with functionalgroups (e.g., acrylic, methacrylic, itaconic acids and their amides).The functional groups may affect a wide range of properties and alsoprovide crosslinking sites. Polar comonomers, in particular carboxylgroups, which are used in comparatively small amounts can have a strongimpact on the adhesion properties. In general, a typical pressuresensitive acrylic polymer composition is derived from the followingmonomers: main monomer (50-98%), modifying monomer (10-40%), and monomerwith functional groups (0.5-20%).

It is commonly known that the adhesion properties of PSAs can be variedby the grafting or crosslinking of polymers. Crosslinking typicallyimproves the creep and shear resistance of PSAs. However, crosslinkingis usually accompanied by a decrease in tack and peel. Generally,crosslinking increases the shear and tensile moduli, and especially itselastic component, at the expense of the viscous one. Thus, there existsa need for PSAs, and methods for producing such PSAs, that exhibitimproved shear strength without a significant reduction in peel andtack.

SUMMARY OF THE INVENTION

In accordance with one embodiment of the present invention, a method ofmaking a modified pressure sensitive adhesive (PSA) is provided. Themethod comprises forming a monomer mixture comprising a main monomer;polymerizing the monomer mixture to thereby form a polymerized mixturecomprising a base polymer having units derived from the main monomer;and after substantial completion of the polymerizing step, reacting amodifying polymer comprising units derived from a n-vinyl lactam withthe polymerized mixture in the presence of a free-radical initiator tothereby form a modified mixture comprising a modified polymer.

In accordance with another embodiment of the present invention, a methodof making a modified PSA is provided. The method comprises forming amonomer mixture comprising an ethylenically unsaturated acid esterhaving a glass transition temperature less than about 0° C. and anethylenically unsaturated acid; emulsion polymerizing the ethylenicallyunsaturated acid ester and the ethylenically unsaturated acid to therebyform an acidic polymerized mixture comprising a base copolymer, whereinthe base copolymer comprises 50 to 98 weight percent of units derivedfrom the ethylenically unsaturated acid ester and 0.1 to 20 weightpercent of units derived from the ethylenically unsaturated acid; afterat least about 80 weight percent of the ethylenically unsaturated acidester has been polymerized, adding polyvinyl pyrrolidone to thepolymerized mixture to thereby form a modified mixture comprising amodified polymer; and neutralizing the modified mixture to a pH of atleast about 7.0 to thereby form a neutralized mixture.

In accordance with still another embodiment of the present invention, amethod of making a modified PSA is provided. The method comprisescopolymerizing a main monomer and a functional monomer via emulsionpolymerization to thereby form a polymeric backbone having a carboxylicfunctional group; and after substantial completion of thecopolymerization step, reacting a polyvinyl pyrrolidone polymer with thepolymeric backbone to thereby chemically bind the polyvinyl pyrrolidonepolymer to the backbone at the carboxylic functional group.

In accordance with yet another embodiment of the present invention, amodified polymer composition suitable for use in PSAs is provided. Themodified polymer composition comprises a polymeric backbone comprisingmain units derived from a main monomer having a glass transitiontemperature of less than about 0° C. in homopolymerized form andfunctional units derived from a functional monomer having a carboxylicfunctionality. The modified polymer composition further comprises amodifying polymeric moiety that has been chemically bound to at leastone of said functional units of said polymeric backbone. Prior to beingchemically bound to the functional unit, the modifying polymeric moietywas a modifying polymer comprising units derived from a n-vinyl lactam.

The inventive modified PSA and process for making such modified PSAprovide an adhesive composition having a substantially improved shearstrength without significant reduction in peel and tack.

DETAILED DESCRIPTION OF THE INVENTION

One embodiment of the present invention concerns a method of making apressure sensitive adhesive (PSA), wherein the method comprises: (1)preparing a monomer mixture comprising one or more polymerizablemonomers; (2) polymerizing the monomer mixture to form a polymerizedmixture; (3) modifying the polymerized mixture with a modifying polymer;and (4) neutralizing the resulting modified mixture.

Generally the monomer(s) employed in the monomer mixture can be anyethylenically unsaturated monomer that is capable of undergoingpolymerization or copolymerization according to the present invention.Examples of suitable ethylenically unsaturated monomers are, forexample, alkyl esters (e.g., (meth)acrylic acid esters); ethylenicallyunsaturated carboxylic acids; the nitriles, vinyl and vinylidenehalides, and amides of unsaturated carboxylic acids; mono- andpolyunsaturated hydrocarbon monomers; vinyl esters (e.g., vinyl estersof C₁ to C₆ saturated monocarboxylic acids); vinyl ethers; and aminomonomers. By convention, the parentheticals used herein designateoptional content (i.e., (meth)acrylate means “acrylate” or“methacrylate”).

Examples of (meth)acrylic acid esters suitable for use in the presentinvention include C₁-C₁₇ alkyl (meth)acrylates. Typical (meth)acrylicesters include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl(meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hexylacrylate, 2-ethylhexyl (meth)acrylate, t-butyl (meth)acrylate,3,3-dimethylbutyl (meth)acrylate, and lauryl acrylate.

Monoethylenically unsaturated monocarboxylic acids suitable for use inthe present invention include (meth)acrylic acid, ethacrylic acid, andcrotonic acid. Suitable monoethylenically unsaturated dicarboxylic acidsinclude maleic acid, fumaric acid, itaconic acid, and citraconic acid.Suitable monoethylenically unsaturated tricarboxylic acids includeaconitic acid and the halogen-substituted derivatives (e.g.,alphachloracylic acid), and the anhydrides of these acids (e.g., maleic.anhydride and citraconic anhydride).

Nitriles of the above ethylenically unsaturated carboxylic acids whichare suitable monomers include acrylonitrile, alpha-chloroacrylonitrile,and methacrylonitrile. Suitable amides of these carboxylic acids includeunsubstituted amides such as (meth)acrylamide and otheralpha-substituted acrylamides and n-substituted amides obtained by thereaction of the amides of the aforementioned carboxylic acids with andanaldehyde (e.g., formaldehyde). Typical n-substituted amides includen-methylolacrylamide, n-methylolmethacrylamide alkylatedn-methylolacrylamides, and n-methylolmethacrylamides (e.g.,n-methyoxymethylacrylamide and n-methoxymethylmethacrylamide). Examplesof vinyl and vinylidene halides include vinyl chloride, vinylidenechloride, vinyl fluoride and vinylidene fluoride.

Examples of suitable hydrocarbon monomers for use in the presentinvention include styrene compounds (e.g., styrene, carboxylatedstyrene, and alpha-methyl styrene), ethylene, propylene, butylene, andconjugated dienes (e.g., butadiene, isoprene and copolymers of butadieneand isoprene).

Suitable vinyl esters for use in the present invention include aliphaticvinyl esters, such as vinyl formate, vinyl acetate, vinyl propionate,vinyl butyrate, vinyl isobutyrate, vinyl valerate, and vinyl caproate,and allyl esters of saturated monocarboxylic acids, such as allylacetate, allyl propionate, and allyl lactate.

Vinyl ethers suitable for use in the present invention includemethylvinyl ether, ethylvinyl ether, and n-butylvinyl ether. Typicallyvinyl ketones include methylvinyl ketone, ethylvinyl ketone, andisobutylvinyl ketone. Suitable dialkyl esters of monoethylenicallyunsaturated dicarboxylic acids include dimethyl maleate, diethylmaleate, dibutyl maleate, dioctyl maleate, diisooctyl maleate, dinonylmaleate, diisodecyl maleate, ditridecyl maleate, dimethyl fumarate,diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dioctyl fumarate,diisooctyl fumarate, didecyl fumarate, dimethyl itaconate, diethylitaconate, dibutyl itaconate, and dioctyl itaconate.

Amino monomers useful in the present invention include substituted andunsubstituted aminoalkyl acrylates, hydrochloride salts of aminomonomers, and methacrylates, such as beta-aminoethylacrylate,beta-amino-ethylnethacrylate, dimethylaminomethylacrylate,beta-methylaminoethylacrylate, and dimethylaminomethylmethacrylate.

In a particularly preferred embodiment of the invention, the monomermixture includes a main monomer and at least one additional monomer thatis copolymerizable with the main monomer.

The “main monomer” employed in the monomer mixture is preferably one ormore ethylenically unsaturated acid esters. More preferably, the mainmonomer is a free-radically polymerizable (meth)acrylate monomer.Examples of suitable (meth)acrylate monomers include acrylate esters ofnon-tertiary alkyl alcohols, the alkyl groups of which have from about 2to about 14 carbon atoms. Examples of such (meth)acrylate monomersinclude, but are not limited to, n-butyl acrylate, 2-ethylhexylacrylate, iso-octyl acrylate (an isomer of 2-ethylhexyl acrylate),4-methyl-2-pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate,sec-butyl acrylate, tert-butyl acrylate, isobornyl acrylate, dodecylacrylate, n-octyl acrylate, tridecyl acrylate, cyclohexyl acrylate,ethoxylated nonyl phenyl acrylate, methyl methacrylate, t-butylmethacrylate, iso-butyl methacrylate, butyl methacrylate, cyclohexylmethyl acrylate, hexyl methacrylate, iso decyl methacrylate, and hexylethyl methacrylate. Preferably, the main monomer, in homopolymerizedform, has a glass transition temperature (T_(g)) (measured bydifferential scanning calorimetry) of less than about 0° C., preferablyless than about −20° C., and most preferably between −60° C. and −30° C.Particularly preferred main monomers suitable for use in the presentinvention include n-butyl acrylate, iso-octyl acrylate, 2-ethylhexylacrylate, ethyl acrylate, n-propyl acrylate, isobutyl acrylate, n-hexylacrylate, lauryl acrylate, n-hexyl methacrylate, and n-octylmethacrylate. More preferably, the main monomer is selected from thegroup consisting of n-butyl acrylate, 2-ethylhexyl acrylate, andiso-octyl acrylate. Most preferably, the main monomer is n-butylacrylate. Generally the amount of the main monomer employed in themonomer mixture of the present invention is in the range of from about40 to about 100 weight percent (by total weight of all the polymerizablemonomers in the monomer mixture), more preferably the main monomer ispresent in the range of from about 60 to about 98 weight percent, andmost preferably from 75 to 95 weight percent.

The “additional monomer(s)” (i.e., the monomer(s) copolymerizable withthe main monomer) employed in the monomer mixture of the presentinvention can generally be categorized as modifying monomers, functionalmonomers, and other miscellaneous monomers.

The “modifying monomer(s)” that can be employed in the present inventionare typically ethylenically unsaturated acid esters having a T_(g) (inhomopolymerized form) greater than the T_(g) (in homopolymerized form)of the main monomer. Preferably, the modifying monomer is a(meth)acrylate monomer having a T_(g) (in homopolymerized form) greaterthan about 0° C., more preferably greater than 20° C. Examples ofsuitable modifying monomers include methyl methacrylate, n-butylmethacrylate, methylacrylate, tert-butyl acrylate, ethyl methacrylate,n-propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate,tert-butyl methacrylate, and n-pentyl methacrylate. Particularlypreferred modifying monomers include methyl methacrylate and n-butylmethacrylate. When a modifying monomer(s) is employed in the monomermixture, it is preferred for the modifying monomer(s) to be present inan amount in the range of from about 0 to about 50 weight percent (basedon the total weight of all the polymerizable monomers in the monomermixture), more preferably the modifying monomer is present in an amountin the range of from about 2 to about 30 weight percent, and mostpreferably in the range of from 5 to 15 weight percent.

The “functional monomer(s)” that can be employed in the presentinvention are typically polar monomers having at least one functionalgroup which readily free-radically copolymerizes with the main monomer.Suitable functional monomers include ethylenically unsaturatedcarboxylic acids (and their salts), ethylenically unsaturated sulfonicacids (and their salts), ethylenically unsaturated phosphonic acids (andtheir salts), ethylenically unsaturated anhydrides, ethylenicallyunsaturated amines and amides, ethylenically unsaturated alcohols, andethylenically unsaturated nitrites. Preferred functional monomersinclude (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid,fumaric acid, vinyl phosphonic acid, 2-acrylamido-2-methylpropylsulfonicacid, maleic anhydride, n,n-dimethylaminoethylacrylate,n,n-dimethylaminoethylmethacrylate, acrylamide, t-butyl acrylamide,n,n-dimethyl amino ethyl acrylamide, n-octyl acrylamide and othern-substituted acrylamides, n,n-dimethylacrylamide and othern,n-disubstituted acrylamides, 2-hydroxyethyl acrylate, 2-hydroxyethylmethacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylates,acrylonitrile, methacrylonitrile, carbowax acrylate,methoxy-ethoxy-ethyl acrylate, mixtures thereof, and the like.Particularly preferred functional monomers include (meth)acrylic acid,itaconic acid, and their amides. Most preferably, the functional monomeris acrylic acid. Generally, it is preferred for the functionalmonomer(s) to have an acid functionality, more preferably the functionalmonomer(s) has a carboxylic functionality. When a functional monomer(s)is employed in the monomer mixture, it is preferred for the functionalmonomer(s) to be present in an amount in the range of from about 0.1 toabout 20 weight percent (based on the total weight of all thepolymerizable monomers in the monomer mixture), more preferably thefunctional monomer is present in an amount in the range of from about0.2 to about 5 weight percent, and most preferably in the range of from0.5 to 2 weight percent.

The “other miscellaneous monomer(s)” that can be employed in the monomermixture of the present invention can be selected from any of a varietyof monomers known to affect the adhesion properties of the finalmodified PSA produced by the present invention. Examples of suitablemiscellaneous monomers include vinyl ester monomers such as, forexample, styrene, vinyl 2-ethylhexanoate, vinyl caprate, vinyl laurate,vinyl pelargonate, vinyl hexanoate, vinyl propionate, vinyl decanoate,and vinyl octanoate. Preferred vinyl ester monomers include styrene,vinyl acetate, vinyl laurate, vinyl caprate, and vinyl-2-ethylhexanoate.When a miscellaneous monomer(s) is employed in the monomer mixture, itis preferred for the miscellaneous monomer(s) to be present in an amountin the range of from about 0 to about 50 weight percent (based on thetotal weight of all the polymerizable monomers in the monomer mixture),more preferably in the range of from 1 to 20 weight percent.

In a preferred embodiment of the invention, the monomer mixture alsocomprises a continuous phase (usually water), a surfactant, and,optionally, a tackifier.

The surfactant can be any conventional surfactant or a combination ofsurfactants known in the art. Generally, the surfactant can be ananionic surfactant or a non-ionic surfactant. Examples of preferredsurfactants include, but are not limited to, alkali alkylsulfate,ammonium alkysulfate, alkylsulfonic acid, fatty acid, oxyethylatedalkyphenol, sulfosuccinates and derivatives, and mixtures thereof. Alist of suitable surfactants is available in the treatise: McCutcheon'sEmulsifiers & Detergents, North American Edition, MC Publishing Co.,Glen Rock, N.J., 1997, the disclosure of which is incorporated herein byreference. The surfactant can also be a polymerizable surfactant whichis a surfactant that contains a polymerizable double bond. Examples ofpolymerizable surfactants include, but are not limited to, HITENOL™BC-10, HITENOL™ HS 20, and HITENOL™ HS 10 surfactants (commerciallyavailable from Dai-ichi Kogyo Seiyaku Co., Kyoto, Japan) and TREM™ LF40surfactant (available from Cognis Corporation, Cincinnati, Ohio). Theamount of surfactant employed in the monomer mixture is generally in therange of from about 0. to about 10 weight percent (based on the totalweight of all the polymerizable monomers in the monomer mixture), morepreferably 0.2 to 5 weight percent, and most preferably 0.5 to 2 weightpercent.

Any tackifier known in the art that can yield the properties desired inthe modified PSA produced by the present invention can be used.Generally, the tackifier can be selected from the group consisting ofrosins, rosin derivatives, rosin esters, hydrocarbon resins, syntheticpolyterpenes, natural terpenes, and the like. More particularly, usefultackifying resins include, but are not limited to, (1) natural andmodified rosins and the hydrogenated derivatives thereof; (2) esters ofnatural and modified rosins and the hydrogenated derivatives thereof;(3) polyterpene resins and hydrogenated polyterpene resins; (4)aliphatic petroleum hydrocarbon resins and the hydrogenated derivativesthereof; (5) aromatic hydrocarbon resins and the hydrogenatedderivatives thereof; and (6) alicyclic petroleum hydrocarbon resins andthe hydrogenated derivatives thereof. Mixtures of two or more of theabove-described tackifiers may be required for some formulations.

Natural and modified rosins and the hydrogenated derivatives thereofinclude, but are not limited to, gum rosin, wood rosin, tall-oil rosin,distilled rosin, hydrogenated rosin, dimerized rosin, and polymerizedrosin. Suitable examples of esters of natural and modified rosins andthe hydrogenated derivatives thereof include, but are not limited to,the glycerol ester of rosin, the glycerol ester of hydrogenated rosin,the glycerol ester of polymerized rosin, the pentaerythritol ester ofhydrogenated rosin. Polyterpene resins generally result from thepolymerization of terpene hydrocarbons, such as the bicyclic monoterpeneknown as pinene, in the presence of Friedel-Crafts catalysts atmoderately low temperatures. Preferably, the polyterpene resins have asoftening point, as determined by ASTM method E28-58T, of from about 80°C. to about 150° C. Aliphatic petroleum hydrocarbon resins andhydrogenated derivatives thereof are generally produced from thepolymerization of monomers consisting of primarily olefins anddiolefins. Preferably, the aliphatic petroleum hydrocarbon resins have aBall and Ring softening point of from about 70° C. to about 135° C.Aromatic hydrocarbon resins include, for example, hydrocarbon resinsderived from at least one alkyl aromatic monomer, such as, for example,styrene, alpha-methyl styrene and vinyl toluene, and the hydrogenatedderivatives thereof. The alkyl aromatic monomers can be obtained frompetroleum distillate fractions or from non-petroleum feedstocks, suchas, for example, feedstocks produced from phenol conversion processes.An alicyclic petroleum hydrocarbon resin can be produced utilizing ahydrocarbon mixture comprising dicyclopentadiene as the monomer.Particularly preferred tackifiers are non-hydrogenated rosin glycerinesters such as, for example, PERMALYN™ 5095 (available from EastmanChemical Company, Kingsport, Tenn.).

The amount of tackifier employed in the monomer mixture is generally inthe range of from about 0.1 to about 10 weight percent (based on thetotal weight of all the polymerizable monomers in the monomer mixture),more preferably 0.2 to 5 weight percent, and most preferably 0.5 to 2weight percent.

Polymerization of the monomer mixture can be performed by anypolymerization process known in the art such as, for example, emulsionpolymerization, solution polymerization, suspension polymerization,micro emulsion polymerization, and inverse emulsion polymerization.However, the method of the present invention is particularly well suitedfor batch or semi-batch free-radical emulsion polymerization.

In accordance with standard procedures, emulsion polymerization of themonomer mixture can be facilitated by free-radical initiators.Initiators used in polymerization processes may be of a type whichproduce free-radicals and conveniently are peroxygen compounds, forexample: inorganic peroxides such as hydrogen peroxide and inorganicpersulfate compounds (e.g., ammonium persulfate, sodium persulfate andpotassium persulfate); organic hydroperoxides such as cumenehydroperoxide and tertiary butyl hydroperoxide; and organic peroxidessuch as benzoyl peroxide, acetyl peroxide, lauroyl peroxide, andperoxydicarbonate esters (e.g., diisopropyl peroxydicarbonate, peraceticacid and perbenzoic acid). Preferably, the initiator is an inorganicpersulfate, most preferably ammonium persulfate. The amount of initiatoremployed during polymerization is preferably in the range of from about0.1 to about 10 weight percent (based on the total weight of allpolymerizable monomers in the monomer mixture), more preferably about0.2 to about 5 Weight percent,- and most preferably 0.5 to 1 weightpercent. The free-radical initiator may be activated by water-solublereducing agents such as ferrous compounds, sodium bisulfite orhydroxylamine hydrochloride, and other free-radical producing materialssuch as 2,2′-azobisisobutyronitrile. The free-radicals required forpolymerization can alternatively be produced via a radiation initiator(e.g., x-rays and UV rays), as known in the art.

Generally, the polymerization of the monomer mixture can be accomplishedvia the continuous addition of the monomer mixture and the initiator toa reaction vessel over a polymerization period of about 0.5 to about 10hours, more preferably 1 to 5 hours. The temperature in the reactionvessel during polymerization of the monomer mixture is preferablymaintained in the range of from about 50° C. to about 120° C., morepreferably about 60° C. to about 100° C., and most preferably 75° C. to90° C. After the desired amount, typically all of the monomer mixturehas been added to the reaction vessel, it is preferred for apost-polymerization period to be employed, during which the remainder ofthe initiator and monomers can be reacted to minimize the amount ofunreacted free monomers left in the polymerized mixture. Typically, thepost-polymerization time period ranges from about 0.2 to about 5.0hours, more preferably 0.5 to 2.0 hours. During the post-polymerizationperiod, the contents of the reaction vessel should be maintained atelevated temperatures, preferably about the same temperatures employedduring polymerization.

During polymerization of the monomer mixture, the monomer(s) of themonomer mixture (i.e., the main monomer and, optionally, the modifying,functional, and/or other miscellaneous monomers) are polymerized to forma base polymer. The base polymer preferably includes a polymericbackbone comprising units derived from the main monomer and, optionally,units derived from the modifying, functional, and/or miscellaneousmonomer(s), described above. The respective amounts (i.e., weightpercents) of units derived from the main, modifying, functional, and/ormiscellaneous monomer(s) present in the polymeric backbone of the basepolymer is preferably the same quantities/ratios employed in the monomermixture, described above. The polymeric backbone preferably includesfunctional groups provided by the functional monomer(s). Morepreferably, the polymeric backbone has an active hydrogen functionality,most preferably the polymeric backbone includes carboxylic functionalgroups provided by the functional monomer. The base polymer preferablyhas a T_(g) of less than about 0° C., more preferably less than about−10° C., and most preferably in the range of from −60° C. to −30° C.

After polymerization of the monomer mixture is substantially complete,the resulting polymerized mixture is modified with a modifying polymer.As used herein, the term “substantially complete” or “substantialcompletion” when used to describe the state of polymerization of themonomer mixture, shall denote a state wherein at least about 50 weightpercent of the main monomer originally present in the monomer mixturehas been polymerized to form the base polymer. Preferably, modificationof the polymerized mixture with the modifying polymer does not takeplace until after at least about 80 weight percent of the main monomerhas been polymerized, most preferably after at least 90 weight percentof the main monomer has been polymerized.

Modification of the base polymer with the modifying polymer, inaccordance with the present invention, can be performed by simply addingthe modifying polymer to the polymerized mixture. The amount ofmodifying polymer added to the polymerized mixture is preferably in therange of from about 0.01 to about 5.0 weight percent (based on the totalweight of all the polymerizable monomers in the monomer mixture), morepreferably about 0.02 to about 2.0 weight percent, still more preferablyabout 0.05 to about 1.0 weight percent, and most preferably 0.075 to 0.5weight percent.

The modifying polymer added to the polymerized mixture afterpolymerization is substantially complete is preferably a polymercomprising units derived from a n-vinyl lactam. More preferably, themodifying polymer comprises at least about 50 mole percent of unitsderived from a n-vinyl lactam. Still more preferably, the modifyingpolymer is a homopolymer of a n-vinyl lactam. Examples of n-vinyllactams that can be used to form the modifying polymer includen-vinyl-2-pyrrolidone, n-vinyl-2-piperidone, n-vinyl-2-caprolactam,n-vinyl-3-methyl-2-pyrrolidone, n-vinyl-3-methyl-2-piperidone,n-vinyl-3-methyl-2-caprolactam, n-vinyl-4-methyl-2-pyrrolidone,n-vinyl-4-methyl-2-caprolactam, n-vinyl-5-methyl-2-pyrrolidone,n-vinyl-5-methyl-2-piperidone, n-vinyl-5,5-dimethyl-2-pyrrolidone,n-vinyl-3,3,5-trimethyl-2-pyrrolidone,n-vinyl-5-methyl-5-ethyl-2-pyrrolidone,n-vinyl-3,4,5-trimethyl-3-ethyl-2-pyrrolidone,n-vinyl-6-methyl-2-piperidone, n-vinyl-6-ethyl-2-piperidone,n-vinyl-3,5-dimethyl-2-piperidone, n-vinyl-4,4-dimethyl-2-piperidone,n-vinyl-7-methyl-2-caprolactam, n-vinyl-7-ethyl-2-caprolactam,n-vinyl-3,5-methyl-2-caprolactam, n-vinyl-4,6-dimethyl-2-caprolactam andn-vinyl-3,5,7-trimethyl-2-caprolactam. If desired, mixtures thereof mayalso be used. It is preferred for the modifying polymer to be apoly(n-vinyl lactam) homopolymer. Particularly preferred poly(n-vinyllactam) homopolymers include polyvinyl pyrrolidone, polyvinylpiperidone, and polyvinyl caprolactam. Most preferably, the modifyingpolymer is a highly water soluble polymer such as a polyvinylpyrrolidone homopolymer. It is preferred for the modifying polymer tohave a T_(g) in the range of from about 50° C. to about 300° C., morepreferably about 100° C. to about 250° C., and most preferably 150° C.to 200° C. It is preferred for the modifying polymer to have an averagemolecular weight in the range of from about 9,000 to about 1,200,000daltons, more preferably about 15,000 to about 100,000 daltons, and mostpreferably 30,000 to 60,000 daltons. It is preferred for the modifyingpolymer to have a K value (indicating intrinsic viscosity) in the rangeof from about 10 to about 100, more preferably about 15 to about 60, andmost preferably 20 to 40.

After and/or while the modifying polymer is added to the polymerizedmixture, it is preferred for the polymerized mixture to be maintained atconditions sufficient to allow the modifying polymer to react with thepolymerized mixture to thereby form a modified mixture comprising amodified polymer. Preferably, the modifying polymer reacts with, andbecomes chemically bound to, the base polymer to produce a modifiedpolymer having an enhanced balance of adhesion properties as compared tothose of the base polymer.

When the modifying polymer is reacted with the polymerized mixture, itis preferred for ring-opening of the modified polymer to occur. In orderfor such ring-opening of the modifying polymer to take place, asufficient amount of a free-radical initiator should be present in thepolymerized mixture along with the modifying polymer. The initiator usedto facilitate ring-opening of the modifying polymer can be the sameinitiator employed to initiate the original polymerization of themonomer mixture, or can be a different initiator capable of generatingfree-radicals. Thus, the initiator can either be added along with themodifying polymer to the polymerized mixture or, alternatively, theinitiator can be left over from the original polymerization of themonomer mixture to form the base polymer. The free-radical initiatorused to facilitate ring-opening of the modifying polymer is preferablythe same type of initiator used to facilitate polymerization of themonomer mixture. Most preferably, the free-radical initiator used forring-opening is an inorganic persulfate such as ammonium persulfate.

Once ring-opening of the modifying polymer has occurred, the ring-openedmodifying polymer can be grafted and/or crosslinked with the polymericbackbone of the base polymer at the locations of the carboxylicfunctional groups. Such grafting and/or crosslinking of the modifyingpolymer with the base polymer produces the modified polymer havingenhanced adhesion properties. Preferably, the modified polymer has aT_(g) of less than about 0° C., more preferably less than about −10° C.,and most preferably in the range of from −60° C. to −20° C.

Conditions sufficient to facilitate the ring-opening, grafting, and/orcrosslinking reactions described above generally include a temperaturein the range of from about 40° C. to about 90° C., more preferably about50° C. to about 80° C., and most preferably 60° C. to 70° C. Thereacting of the modifying polymer with the polymerized mixture can becarried out a pressure in the range of from about 0.5 to about 2 bar,preferably about 0.8 to about 1.5 bar, and most preferably aboutatmospheric pressure. It is preferred for the reacting of the modifyingpolymer with the polymerized mixture to be carried out under mixingconditions for a time period in the range of from about 0.01 to about 2hours, more preferably from 0.05 to 0.5 hours. It is also preferred forthe reacting of the modifying polymer with the base polymer to beperformed in an acidic environment. Thus, the polymerized mixture towhich the modifying polymer is added preferably has a pH of less thanabout 5.0, more preferably less than about 4.0, and most preferably inthe range from 1.0 to 3.0.

The resulting modified mixture containing the modified polymer typicallyhas a pH of less than about 6.0, more typically less than about 5.0, andmost typically in the range of from about 1.0 to 4.0. After the modifiedmixture is formed, it is preferred to neutralize the modified mixture byincreasing its pH with a neutralent to at least about 7.0, morepreferably in the range of about 8.0 to about 9.0, and most preferably8.25 to 8.75. Neutralents to be added to the modified mixture can be anyneutralent known in the art. Suitable neutralents include, but are notlimited to, alkylihydroxides and amines. Examples of alkylihydroxidesinclude sodium hydroxide, potassium hydroxide, and lithium hydroxide.Examples of amines include ethanol amine, triethylamine, anddimethylethanolamine. A particularly preferred neutralent is ammonia.

In a preferred embodiment of the present invention, a further quantityof the modifying polymer can be added to the neutralized mixture toimprove the rheological properties of the final PSA. When the modifyingpolymer is added to the neutralized mixture, it is preferred for themodifying polymer to be added in an amount in the range of from about0.01 to about 2.0 percent (by weight of the modified polymer present inthe neutralized mixture), more preferably 0.05 to 1.0 weight percent.

Various formulating agents may be added to the neutralized mixture(typically a latex) of the present invention. Suitable additivesinclude, but are not limited to, defoamers, wetting agents, thickeners,protective colloids, tackifiers, fillers and/or extenders such asdispersible clays, colorants such as pigments and dyes, solvents,plasticizers, coalescing agents, preservative agents such as biocides,fungicides, and mildewcides, buffers, agents to adjust pH, surfactants,and catalysts.

The PSA compositions according to the invention can be used to make asubstrate bearing a coating of a PSA. The method comprises applying anadhesive composition to a surface of a substrate, wherein the adhesivecomposition is made in accordance with the process described above.

The PSAs of the present invention can be applied to any backing which itis desired to adhere to another surface or article. Illustrativebackings include flexible and rigid (solid), natural and syntheticmaterials such as plastics, elastomers, solid metals and foils, ceramics(tiles, glass, and the like), wood, papers and cardboard, leathermaterials, etc. of essentially any form including films, solid articles,woven and non-woven textile materials, and the like. Illustrative usesof such articles include wall coverings (paper, fabric, films, and thelike), upholstery items, construction roofing and siding materials,tapes of all varieties (including those having backings comprised ofwoven or non-woven fabrics, paper, polymeric films, metal foils, foams,etc., including double-faced tapes and so-called transfer tapes),packaging, floor and wall tile, other floor and wall coverings, andpaneling, and the like.

Suitable backing and substrate materials can be of essentially anychemical composition and include, for example, metals, ceramics(including glass), and natural and synthetic polar and non-polarmaterials such as polyolefins, e.g., homopolymers and interpolymers ofsubstituted and nonsubstituted olefinically unsaturated hydrocarbonsincluding ethylene, propylene, styrene, butadiene, dicyclopentadiene,etc., and materials which typically contain polar functional groups suchas hydroxy, etheral, carbonyl, carboxylic acid (including carboxylicacid salts), carboxylic acid esters (including thio esters), amides,amines, and the like. Essentially all natural materials include one ormore polar functional groups. Illustrative are virgin and reclaimedcellulosic fibers such as cotton, paper, wood, coconut fiber, jute,hemp, and the like, and proteinaceous materials such as leather, wool,and other animal fur. Illustrative synthetic materials containing polarfunctional groups are polyesters, polyamides, and carboxylatedstyrene-butadiene polymers. Illustrative of other useful materials whichare also polar are synthetic carbon, silicon, and magnesium silicate(e.g., asbestos). Preferred substrates or backings for the adhesivecomposition of the present invention are polypropylene, polyethylene,polyethylene terephthalate, and polyvinyl chloride.

The modified PSA composition of the present invention may be applied tothe backing by any one of a variety of conventional coating techniquessuch as roll coating, spray coating, and curtain coating. They also maybe applied to the backing by extrusion coating, coextrusion, and hotmelt coating by employing suitable conventional coating devices knownfor such coating methods. While primers may be employed to pretreat thebacking, they are unnecessary in many applications. Dry coating weight(the weight of dry adhesive applied per unit surface area) can varysubstantially depending upon the porosity and irregularity of thebacking and of the substrate surface to which the backing is to beadhered, and other factors. For instance, higher polymer loadings arepreferred for adhering porous, irregular ceramic tiles to poroussurfaces, while lower adhesive loadings are usually required tomanufacture tapes, films, and other articles from relatively non-porous,smooth-surfaced materials such as synthetic polymer films and sheets.

The inventive PSAs (hereinafter referred to as “modified PSAs”) formedfrom the modified polymer, described above, generally exhibit a superiorbalance of adhesion properties versus conventional PSAs (hereinafterreferred to as “unmodified PSAs”) formed from the unmodified basepolymer, also described above. Generally, the modified PSAs exhibitsuperior shear strength and transfer on steel properties, with similartack and peel properties relative to unmodified PSAs. The test methodsused to determine shear strength, transfer on steel, tack, and peelproperties are standard test methods described in detail below in the“Test Methods” section. Preferably, the shear strength of the modifiedPSA is at least about 25 percent greater than the shear strength of theunmodified PSA, more preferably at least about 50 percent greater, andmost preferably at least 75 percent greater. Generally, the shearstrength of the modified PSA will be greater than about 1,000 minutes,more preferably greater than about 1,500 minutes, still more preferablygreater than about 2,000 minutes, and most preferably greater than 3,000minutes. Preferably, the transfer on steel of the modified PSA is lessthan the transfer on steel of the unmodified PSA, more preferably thetransfer on steel of the modified PSA is at least about 10 percent lessthan the transfer on steel of the unmodified PSA, most preferably atleast 25 percent less. Generally, the transfer on steel of the modifiedPSA will be less than about 50 percent, more preferably less than about30 percent, and most preferably less than 20 percent. Preferably, therolling ball tack, loop tack, and peel strength of the modified PSA willbe within about 50 percent of the rolling ball tack, loop tack, and peelstrength of the unmodified PSA, respectively, more preferably withinabout 35 percent, and most preferably within 25 percent. Generally, therolling ball tack of the modified PSA will be in the range of from about2 to about 4 centimeters, more preferably 2.5 to 3.5 centimeters.Generally, the loop tack of the modified PSA will be in the range offrom about 6 to about 12 N/2.5cm, more preferably from about 7 to about11 N/2.5cm, and most preferably 7.5 to 9.5 N/2.5cm. Generally the peelstrength of the modified PSA will be in the range of from about 5 toabout 15 N/2.5cm, most preferably 6 to 12 N/2.5cm.

The present invention is described in greater detail in the followingexamples. The following test methods have been employed in the examples.

Test methods

1. Test samples were prepared by applying to a 25 μm bi-axially orientedpolypropylene (BOPP) backing with corona treatment (38 mN/m), a film ofadhesive latex which, when cured, forms a 20 g/m² dry deposit. Emulsionpolymers were applied in layer of 80 μm and dried at 105° C. (221° F.)for 3 minutes covered with release liner and aged 24 hours at 23±2° C.(73.4±3.4° F.) and 50±5% relative humidity.

2. Shear strength was determined in accordance with PSTC-7 (“PressureSensitive Tape Council”) and is a measure of the cohesive strength of anadhesive. This method is used to determine the shear resistance of apressure sensitive adhesive under a constant load. It is based on thetime required for a static loaded tape sample to separate from astandard flat surface in a direction essentially parallel to the surfaceto which it has been fixed with a standard pressure. A coated strip(2.5×2.5 cm) is applied to a stainless steel plate and a 1,000 gramweight is attached to the bottom of the film. The steel panel with thecoated strip attached is held in a rack such that the panel forms anangle of 178° to 180°. The time, in minutes, required to total failureof the test strip at 23° C. is recorded as the shear strength.

3. Peel strength was determined in accordance with PSTC-1 and is ameasure of the force required to remove a pressure sensitive tape from astainless steel panel at a specified angle (180°) and speed (300mm/min.). A 2.5 cm width of coated sheet is applied to a horizontalsurface of a clean, stainless steel test plate with at least 16 cm ofcoated sheet material in firm contact with the steel plate. A hardrubber roller is used to firmly apply the strip and remove alldiscontinuities and entrapped air. The free end of the coated strip isthen doubled back nearly touching itself so that the angle of removalfrom the steel plate will be 180° C. The steel panel and the free end ofthe coated strip is then attached to the jaw of tensile tester. The jawwith free end of coated strip moves away at the rate of 300 mm perminute. The force, in N/2.5 cm, required to remove the coated strip isrecorded as the peel strength.

4. Rolling Ball Tack was determined in accordance with PSTC-6. Therolling ball tack test is designed to measure the softness to a pressuresensitive adhesive. In the determination of tack by rolling ball method,a steel ball is released at the top of an incline, allowed to acceleratedown the incline and roll onto a horizontal surface covered with apressure sensitive adhesive (30×5 cm). The distance that the stainlesssteel ball travels on the adhesive film is measured and recorded as therolling ball tack.

5. Loop Tack was determined in accordance with FINAT-9 (FINAT TechnicalHandbook, 5^(th) Edition, 1999, pp. 22-24, incorporated herein byreference). It determines the force required to break the bond that isformed when a pressure sensitive adhesive is brought into contact with atest surface from stainless steel. A loop of coated strip (17.5×2.5 cm)with adhesive outermost is attached to the flexible jaw of tensiletester and then it is brought into the contact with stainless steelplate (2.5 cm width). When full contact over the plate is achieved(2.5×2.5 cm) immediately reverse the direction of the machine and allowseparation to take place at a speed of 300 mm per minute. Maximum forcenecessary to completely separation of the loop from the stainless steelplate is recorded as the loop tack.

6. Transfer onto steel was monitored during the peel strength test andwas interpreted as an amount of adhesive, which was transferred fromsubstrate onto steel in percentage.

EXAMPLE 1

Preparation of Sample 1 (Comparative)

An acrylic emulsion polymer was prepared from a monomer mixturecontaining 470 grams of water, 29 grams of a 30% solution of fattyalcohol ether (12 EO units) sulfate Na salt (DISPONIL™ FES 993 IS,available from Cognis Corporation, Cincinnati, Ohio), 947 grams ofn-butyl acrylate, 75 grams of butyl methacrylate, 12.4 grams of acrylicacid, and 3.5 grams of modified polyalkylene glycol (cosurfactant)(DEHYDRAN™ 240, available from Cognis). The kettle containing 276 gramsof water was heated to 80° C. An initiator charge of 0.85 grams ofammonium persulfate dissolved in 10 grams of water and 2.0 grams ofsodium metabisulphite dissolved in 18.7 grams of water were added. Themonomer emulsion was then gradually added over a three hour period alongwith 7.5 grams of ammonium persulfate dissolved in 85.5 grams of waterin a separate feed. After the three hour period emulsion was heated foradditional hour at 85° C. After that the latex was cooled to 40° C. atwhich point latex was neutralized with aqueous ammonia to achieve a pHvalue of 8.5. Consecutively wetting agent (DEHYDRAN™ 240) and defoamer(FOAMASTER™ 306, available from Cognis) were added. The wetting agentwas added in a 0.5 to 2.0 percent quantity, based on the weight of thefinal product. The defoamer was added in a 0.1 to 0.5 percent quantity,based on the weight of the final product. The latex was then cooled toambient temperature.

EXAMPLE 2

Preparation of Sample 2

An acrylic emulsion polymer was prepared in a similar manner to Sample 1using a monomer mixture containing 470 grams of water, 29 grams of a 30%solution of fatty alcohol ether (12 EO units) sulfate Na salt (DISPNIL™FES 993 IS), 947 grams of n-butyl acrylate, 75 grams of butylmethacrylate, 12.4 grams of acrylic acid, and 3.5 grams of modifiedpolyalkylene glycol (cosurfactant) (DEHYDRAN™ 240). The kettlecontaining 276 grams of water was heated to 80° C. An initiator chargeof 0.85 grams of ammonium persulfate dissolved in 10 grams of water and2.0 grams of sodium metabisulphite dissolved in 18.7 grams of water wereadded. The monomer emulsion was then gradually added over a three hourperiod along with 7.5 grams of ammonium persulfate dissolved in 85.5grams of water in a separate feed. After the three hour period emulsionwas heated for additional hour at 85° C. After that the emulsion wascooled to 65° C. at which point latex was treated with 3.1 grams ofpolyvinylpyrrolidone (LUVISKOL™ K30, available from BASF Corporation,Mount Olive, N.J.) dissolved in 9.3 grams of water. The emulsion wasmixed for 10 minutes and cooled to 40° C. and neutralized with aqueousammonia to achieve a pH value of 8.5. Consecutively wetting agent(DEHYDRAN™ 240) and defoamer (FOAMASTER™ 306) were added. The wettingagent was added in a 0.5 to 2.0 percent quantity, based on the weight ofthe final product. The defoamer was added in a 0.1 to 0.5 percentquantity, based on the weight of the final product. The latex was thencooled to ambient temperature.

EXAMPLE 3

Preparation of Sample 3

Sample 3 was prepared in a similar manner to Sample 2 using a monomermixture containing 470 grams of water, 29 grams of a 30% solution offatty alcohol ether (12 EO units) sulfate Na salt (DISPONIL™ FES 993IS), 947 grams of n-butyl acrylate, 75 grams of butyl methacrylate, 12.4grams of acrylic acid, and 3.5 grams of modified polyalkylene glycol(cosurfactant) (DEHYDRAN™ 240). The kettle containing 276 grams of waterwas heated to 80° C. An initiator charge of 0.85 grams of ammoniumpersulfate dissolved in 10 grams of water and 2.0 grams of sodiummetabisulphite dissolved in 18.7 grams of water were added. The monomeremulsion was then gradually added over a three hour period along with7.5 grams of ammonium persulfate dissolved in 85.5 grams of water in aseparate feed. After the three hour period emulsion was heated foradditional hour at 85° C. After that the emulsion was cooled to 65° C.at which point latex was treated with 3.1 grams of polyvinylpyrrolidone(LUVISKOL™ K30) dissolved in 9.3 grams of water. The emulsion was mixedfor 10 minutes and cooled to 40° C. and neutralized with aqueous ammoniato achieve a pH value of 8.5. After neutralization 5.2 grams ofpolyvinylpyrrolidone dissolved in 9.3 grams of water was added to thelatex and consecutively wetting agent (DEHYDRAN™ 240) and defoamer(FOAMASTER™ 306) were added. The wetting agent was added in a 0.5 to 2.0percent quantity, based on the weight of the final product. The defoamerwas added in a 0.1 to 0.5 percent quantity, based on the weight of thefinal product. The latex was then cooled to ambient temperature. TABLE 1Transfer Peel onto R.B.T. Strength Loop Tack Shear Steel (cm) (N/2.5 cm)(N/2.5 cm) (min.) (%) Sample 1 2.8 11.5 9.5 620 50 (comp.) Sample 2 2.910.7 8.4 >1440 26 Sample 3 3.3 8.4 8.4 >1440 0

EXAMPLE 4

Preparation of Sample 4 (Comparative)

An acrylic emulsion polymer was prepared from a monomer mixturecontaining 412 grams of water, 35.2 grams of a 30% solution of fattyalcohol ether (30 EO units) sulfate Na salt (DISPONIL™ FES 77 IS,available from Cognis), 10.4 grams of a 30% solution of fatty alcoholether (12 EO units) sulfate Na salt (DISPONIL™ FES 993 IS), 959 grams ofn-butyl acrylate, 73 grams of methyl methacrylate and 10.4 grams ofacrylic acid. The kettle containing 202 grams of water was heated to 80°C. An initiator charge of 1.2 grams of ammonium persulfate dissolved in15.4 grams of water and 0.5 grams of sodium metabisulphite dissolved in20.3 grams of water were added. The monomer emulsion was then graduallyadded over a three hour period along with 7.1 grams of ammoniumpersulfate dissolved in 88.3 grams of water and with 1.6 grams of sodiummetabisulphite dissolved in 61 grams of water in a separate feeds. Afterthe three hour period emulsion was heated for additional hour at 85° C.After that the latex was cooled to 40° C. at which point latex wasneutralized with aqueous ammonia to achieve a pH value of 8.5.Consecutively wetting agent (DEHYDRAN™ 240) and defoamer (FOAMASTER™306) and thickener (RHEOLATE™ 350, available from Elementis Specialties,Hightstown, N.J.) were added. The wetting agent was added in a 0.5 to.2.0 percent quantity, based on the weight of the final product. Thedefoamer was added in a 0.1 to 0.5 percent quantity, based on the weightof the final product. The thickener was added in a 0.1 to 1.5 percentquantity, based on the weight of the final product. The latex was thencooled to ambient temperature.

EXAMPLE 5

Preparation of Sample 5

Sample 5 was prepared in a similar manner to Sample 4 using a monomermixture containing 412 grams of water, 35.2 grams of a 30% solution offatty alcohol ether (30 EO units) sulfate Na salt (DISPONIL™ FES 77 IS),10.4 grams of a 30% solution of fatty alcohol ether (12 EO units)sulfate Na salt (DISPONIL™ FES 993 IS), 959 grams of n-butyl acrylate,73 grams of methyl methacrylate and 10.4 grams of acrylic acid. Thekettle containing 202 grams of water was heated to 80° C. An initiatorcharge of 1.2 grams of ammonium persulfate dissolved in 15.4 grams ofwater and 0.5 grams of sodium metabisulphite dissolved in 20.3 grams ofwater were added. The monomer emulsion was then gradually added over athree hour period along with 7.1 grams of ammonium persulfate dissolvedin 88.3 grams of water and with 1.6 grams of sodium metabisulphitedissolved in 61 grams of water in a separate feed. After the three hourperiod emulsion was heated for additional hour at 85° C. After that theemulsion was cooled to 65° C. at which point latex was treated with 1.0gram of polyvinylpyrrolidone (LUVISKOL™ K30) dissolved in 9.3 grams ofwater. The emulsion was mixed for 10 minutes and cooled to 40° C. andneutralized with aqueous ammonia to achieve a pH value of 8.5. Afterneutralization 1.6 grams of polyvinylpyrrolidone (as above) dissolved in14.1 grams of water was added to the latex and consecutively wettingagent (DEHYDRAN™ 240), defoamer (FOAMASTER™ 306) and thickener(RHEOLATE™ 350) were added. The wetting agent was added in a 0.5 to 2.0percent quantity, based on the weight of the final product. The defoamerwas added in a 0.1 to 0.5 percent quantity, based on the weight of thefinal product. The thickener was added in a 0.1 to 1.5 percent quantity,based on the weight of the final product. The latex was then cooled toambient temperature.

EXAMPLE 6

Preparation of Sample 6 (Internally Tackified Latex)

Sample 6 was prepared in a similar manner to Sample 4 using a monomermixture containing 412 grams of water, 35.2 grams of a 30% solution offatty alcohol ether (30 EO units) sulfate Na salt (DISPONIL™ FES 77 IS),10.4 grams of a 30% solution of fatty alcohol ether (12 EO units)sulfate Na salt (DISPONIL™ FES 993 IS), 823 grams of n-butyl acrylate,73 grams of methyl methacrylate and 10.4 grams of acrylic acid. To thismonomer mixture 10.4 grams of tackifier (PERMALYN™ 5095, available fromEastman Chemical Company, Kingsport, Tenn.) dissolved in 120 grams ofn-butyl acrylate was slowly added under agitation. The kettle containing202 grams of water was heated to 80° C. An initiator charge of 1.2 gramsof ammonium persulfate dissolved in 15.4 grams of water and 0.5 grams ofsodium metabisulphite dissolved in 20.3 grams of water were added. Themonomer emulsion was then gradually added over a three hour period alongwith 7.1 grams of ammonium persulfate dissolved in 88.3 grams of waterand with 1.6 grams of sodium metabisulphite dissolved in 61 grams ofwater in a separate feeds. After the three hour period emulsion washeated for additional hour at 85° C. After that the latex was cooled to40° C. at which point latex was neutralized with aqueous ammonia toachieve a pH value of 8.5. Consecutively wetting agent (DEHYDRAN™ 240)and defoamer (FOAMASTER™ 306) and thickener (RHEOLATE™ 350) were added.The wetting agent was added in a 0.5 to 2.0 percent quantity, based onthe weight of the final product. The defoamer was added in a 0.1 to 0.5percent quantity, based on the weight of the final product. Thethickener was added in a 0.1 to 1.5 percent quantity, based on theweight of the final product. The latex was then cooled to ambienttemperature.

EXAMPLE 7

Preparation of Sample 7 (Internally Tackified Latex)

Sample 7 was prepared in a similar manner to Sample 6 using a monomermixture containing 412 grams of water, 35.2 grams of a 30% solution offatty alcohol ether (30 EO units) sulfate Na salt (DISPONIL™ FES 77 IS),10.4 grams of a 30% solution of fatty alcohol ether (12 EO units)sulfate Na salt (DISPONIL™ FES 993 IS), 823 grams of n-butyl acrylate,73 grams of methyl methacrylate and 10.4 grams of acrylic acid. To thismonomer mixture 10.4 grams of tackifier (PERMALYN™ 5095) dissolved in120 grams of n-butyl acrylate was slowly added under agitation. Thekettle containing 202 grams of water was heated to 80° C. An initiatorcharge of 1.2 grams of ammonium persulfate dissolved in 15.4 grams ofwater and 0.5 grams of sodium metabisulphite dissolved in 20.3 grams ofwater were added. The monomer emulsion was then gradually added over athree hour period along with 7.1 grams of ammonium persulfate dissolvedin 88.3 grams of water and with 1.6 grams of sodium metabisulphitedissolved in 61 grams of water in a separate feeds. After that theemulsion was cooled to 65° C. at which point latex was treated with 1.0gram of polyvinylpyrrolidone (LUVISKOL™ K30) dissolved in 9.3 grams ofwater. The emulsion was mixed for 10 minutes and cooled to 40° C. andneutralized with aqueous ammonia to achieve a pH value of 8.5. Afterneutralization 1.6 grams of polyvinylpyrrolidone (LUVISKOL™ K30)dissolved in 14.1 grams of water was added to the latex andconsecutively wetting agent (DEHYDRAN™ 240), defoamer (FOAMASTER™ 306)and thickener (RHEOLATE™ 350) were added. The wetting agent was added ina 0.5 to 2.0 percent quantity, based on the weight of the final product.The defoamer was added in a 0.1 to 0.5 percent quantity, based on theweight of the final product the thickener was added in a 0.1 to 1.5percent quantity, based on the weight of the final product. The latexwas then cooled to ambient temperature. TABLE 2 R.B.T. Peel StrengthLoop Tack Shear (cm) (N/2.5 cm) (N/2.5 cm) (min.) Sample 4 (comp.) 3.07.4 8.0 996 Sample 5 3.3 6.8 8.1 >1440 Sample 6 2.1 9.6 8.0 716 Sample 72.9 11.2 9.0 >1440 (3500)

EXAMPLE 8

Samples 8-19 were prepared in a similar manner to Sample 7, butdifferent tackifiers were used instead of PERMALYN™ 5095. TABLE 3Tackifier Description of Tackifier Sample 7 PERMALYN ™ 5095 rosin,glycerin ester, non-hydrogenated Sample 8 HERCULES ™ AR 100 modifiedaromatic resin Sample 9 EASTOTACKT ™ H 100 R aliphatic hydrocarbon resinSample 10 HERCOTACK ™ 205 modified aliphatic hydro- carbon resin Sample11 HERCULES ™ A 101 aromatic hydrocarbon resin Sample 12 STAYBELITE ™ E10 rosin, glycerin ester, partially hydrogenated Sample 13 PICCOTACK ™95 E aliphatic hydrocarbon resin Sample 14 REGALITE ™ R 91 hydrocarbonresin, totally hydrogenated Sample 15 HERCULES ™ MBG 246 hydrocarbonresin, partially hydrogenated Sample 16 REGALITE ™ R 101 hydrocarbonresin, totally hydrogenated Sample 17 HERCULES ™ MBG 275 hydrocarbonresin, partially hydrogenated Sample 18 PERMALYN ™ 5110 rosin,pentaerythrite ester, non-hydrogenated Sample 19 PERMALYN ™ 6110 rosin,pentaerythrite ester, non-hydrogenated

TABLE 4 Peel Strength Loop Tackifier (N/ Tack (N/ Shear (1%/monomers)2.5 cm) 2.5 cm) (min.) Sample 7 PERMALYN ™ 5095 11.2 9.0 >1440 (3500)Sample 8 HERCULES ™ AR 100 6.1 5.6 >1440 Sample 9 EASTOTACK ™ H 100 R7.7 5.2 >1440 Sample 10 HERCOTACK ™ 205 7.3 6.7 >1440 Sample 11HERCULES ™ A 101 7.4 5.8 >1440 Sample 12 STAYBELITE ™ E 10 8.0 6.1 >1440Sample 13 PICCOTACK ™ 95 E 6.6 4.5 >1440 Sample 14 REGALITE ™ R 91 8.06.3 >1440 Sample 15 HERCULES ™ MBG 246 8.2 4.8 >1440 Sample 16REGALITE ™ R 101 7.4 6.5 >1440 Sample 17 HERCULES ™ MBG 275 8.12.5 >1440 Sample 18 PERMALYN ™ 5110 8.3 6.6 >1440 Sample 19 PERMALYN ™6110 8.5 4.7 >1440

1-25. (canceled)
 26. A method of making a pressure sensitive adhesivecomprising: forming a monomer mixture comprising an ethylenicallyunsaturated acid ester having a glass transition temperature of lessthan about 0° C. and an ethylenically unsaturated acid; emulsionpolymerizing said ethylenically unsaturated acid ester and saidethylenically unsaturated acid to thereby form an acidic polymerizedmixture comprising a base copolymer, wherein said base copolymercomprises about 60 to about 98 weight percent of units derived from saidethylenically unsaturated acid ester and about 0.2 to about 5 weightpercent of units derived from said ethylenically unsaturated acid; afterat least about 80 weight percent of said ethylenically unsaturated acidester has been polymerized, adding polyvinyl pyrrolidone to said acidicpolymerized mixture to thereby form a modified mixture comprising amodified polymer; and neutralizing said modified mixture to a pH of atleast about 7.0 to thereby form a neutralized mixture:
 27. The method ofclaim 26 wherein said ethylenically unsaturated acid ester has a glasstransition temperature of less than about −20° C. in homopolymerizedform.
 28. The method of claim 27 wherein said ethylenically unsaturatedacid ester is n-butyl acrylate and said ethylenically unsaturated acidis acrylic acid.
 29. The method of claim 28 wherein said monomer mixturefurther comprises an ethylenically unsaturated acid ester having a glasstransition temperature of at least 20° C. in homopolymerized form. 30.The method of claim 26 further comprising reacting said polyvinylpyrrolidone with said base copolymer to thereby form said modifiedpolymer.
 31. The method of claim 30 wherein said emulsion polymerizingstep includes employing a free-radical initiator to initiatepolymerization.
 32. The method of claim 31 wherein said reacting stepincludes using said free-radical initiator to facilitate ring-opening ofsaid polyvinyl pyrrolidone.
 33. The method of claim 32 wherein saidfree-radical initiator is an inorganic persulfate.
 34. The method ofclaim 30 wherein said reacting step includes chemically binding saidpolyvinyl pyrrolidone with said base copolymer.
 35. The method of claim26 wherein said adding step includes adding about 0.2 to about 2.0weight percent, based on the total weight of monomers in said monomermixture, of said polyvinyl pyrrolidone to said acidic polymerizedmixture.
 36. The method of claim 26 wherein said adding step includesadding 0.075 to 0.5 weight percent, based on the total weight ofmonomers in said monomer mixture, of said polyvinyl pyrrolidone to saidacidic polymerized mixture.
 37. The method of claim 26 furthercomprising adding polyvinyl pyrrolidone to said neutralized mixture. 38.A pressure sensitive adhesive composition produced by the method ofclaim
 26. 39. A method of making a pressure sensitive adhesivecomprising: copolymerizing a main monomer and a functional monomer viaemulsion polymerization to thereby form a polymeric backbone having acarboxylic functional group; and after substantial completion of saidcopolymerization step, reacting a polyvinyl pyrrolidone polymer withsaid polymeric backbone to thereby chemically bind said polyvinylpyrrolidone polymer to said backbone at said carboxylic functionalgroup.
 40. The method of claim 39 wherein said copolymerizing andreacting steps are carried out in the presence of a free-radicalinitiator.
 41. The method of claim 40 wherein said free-radicalinitiator is a peroxide.
 42. The method of claim 41 wherein saidfree-radical initiator is ammonium persulfate.
 43. The method of claim39 wherein said reacting step includes ring-opening of said polyvinylpyrrolidone polymer.
 44. The method of claim 39 wherein said reactingstep includes grafting said polyvinyl pyrrolidone polymer onto saidpolymeric backbone.
 45. The method of claim 39 wherein said reactingstep includes crosslinking said polymeric backbone with said polyvinylpyrrolidone polymer.
 46. The method of claim 39 wherein said polymericbackbone comprises about 60 to about 98 weight percent of units derivedfrom said main monomer and about 0.2 to about 5 weight percent of unitsderived from said functional monomer.
 47. The method of claim 46 whereinsaid main monomer is an ethylenically unsaturated acid ester and saidfunctional monomer is an ethylenically unsaturated acid.
 48. The methodof claim 46 wherein said main monomer is a (meth)acrylate monomer havinga glass transition temperature less than about 0° C. in homopolymerizedform and said functional monomer is a carboxylic acid.
 49. The method ofclaim 46 wherein said main monomer is n-butyl acrylate and saidfunctional monomer is acrylic acid.
 50. The method of claim 39 whereinsaid copolymerizing step includes copolymerizing a modifying monomerhaving a glass transition temperature of at least about 0° C. inhomopolymerized form with said main monomer and said functional monomer.51. The method of claim 50 wherein said polymeric backbone comprisesabout 60 to about 98 weight percent of units derived from said mainmonomer, about 2 to about 30 weight percent of units derived from saidmodifying monomer, and about 0.2 to about 5 weight percent of unitsderived from said functional monomer.
 52. The method of claim 51 whereinsaid modifying monomer is a (meth)acrylate monomer having a glasstransition temperature of at least 20° C.
 53. The method of claim 51wherein said main monomer is n-butyl acrylate, said functional monomeris acrylic acid, and said modifying monomer is butyl methacrylate ormethyl methacrylate.
 54. The method of claim 39 wherein said reactingstep is performed in an acidic environment.
 55. A pressure sensitiveadhesive composition produced by the method of claim
 39. 56. A modifiedpolymer composition suitable for use in pressure sensitive adhesives,said modified polymer composition comprising: a polymeric backbonecomprising main units derived from a main monomer having a glasstransition temperature of less than about 0° C. in homopolymerized formand functional units derived from a functional monomer having acarboxylic functionality; and a modifying polymeric moiety that has beenchemically bound to at least one of said functional units of saidpolymeric backbone, wherein prior to being chemically bound to said atleast one functional unit said modifying polymeric moiety was amodifying polymer comprising units derived from a n-vinyl lactam. 57.The modified polymer composition of claim 56 wherein said n-vinyl lactamis selected from the group consisting of n-vinyl pyrrolidone, n-vinylcaprolactam, and n-vinyl piperidone.
 58. The modified polymercomposition of claim 56 wherein said modifying polymer is a poly(n-vinyllactam) homopolymer.
 59. The modified polymer composition of claim 56wherein said modifying polymer comprises at least about 50 mole percentof units derived from n-vinyl pyrrolidone.
 60. The modified polymercomposition of claim 56 wherein said modifying polymer is a polyvinylpyrrolidone homopolymer.
 61. The modified polymer composition of claim56 wherein said polymeric backbone and said modifying polymer were eachformed in separate polymerization procedures.
 62. The modified polymercomposition of claim 61 wherein said polymeric backbone was formed viaemulsion polymerization.
 63. The modified polymer composition of claim56 wherein said polymeric backbone comprises about 60 to about 98 weightpercent of units derived from said main monomer and about 0.2 to about 5weight percent of units derived from said functional monomer.
 64. Themodified polymer composition of claim 63 wherein said main monomer isn-butyl acrylate and said functional monomer is acrylic acid.
 65. Themodified polymer composition of claim 56 wherein said copolymerizingstep includes copolymerizing a modifying monomer having a glasstransition temperature of at least about 0° C. in homopolymerized formwith said main monomer and said functional monomer.
 66. The modifiedpolymer composition of claim 65 wherein said polymeric backbonecomprises about 60 to about 98 weight percent of units derived from saidmain monomer, about 2 to about 30 weight percent of units derived fromsaid modifying monomer, and about 0.2 to about 5 weight percent of unitsderived from said functional monomer.
 67. The modified polymercomposition of claim 66 wherein said modifying monomer is a(meth)acrylate monomer having a glass transition temperature of at least20° C.
 68. The modified polymer composition of claim 66 wherein saidmain monomer is n-butyl acrylate, said functional monomer is acrylicacid, and said modifying monomer is butyl methacrylate or methylmethacrylate.
 69. The modified polymer composition of claim 56 having aglass transition temperature of less than about −10° C.
 70. The modifiedpolymer composition of claim 69 having a glass transition temperature of−60° C. to −20° C.